CN114843467A - Nitrogen-phosphorus co-doped vanadium oxide/carbon self-supporting electrode material and preparation method and application thereof - Google Patents
Nitrogen-phosphorus co-doped vanadium oxide/carbon self-supporting electrode material and preparation method and application thereof Download PDFInfo
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- 239000007772 electrode material Substances 0.000 title claims abstract description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 24
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910001935 vanadium oxide Inorganic materials 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
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- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 21
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- 238000007254 oxidation reaction Methods 0.000 claims description 12
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
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- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- FSJSYDFBTIVUFD-SUKNRPLKSA-N (z)-4-hydroxypent-3-en-2-one;oxovanadium Chemical compound [V]=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FSJSYDFBTIVUFD-SUKNRPLKSA-N 0.000 claims description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- 239000002033 PVDF binder Substances 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
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- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
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- 230000001590 oxidative effect Effects 0.000 abstract description 6
- 230000007547 defect Effects 0.000 abstract description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
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- CITILBVTAYEWKR-UHFFFAOYSA-L zinc trifluoromethanesulfonate Substances [Zn+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F CITILBVTAYEWKR-UHFFFAOYSA-L 0.000 description 2
- SKKMWRVAJNPLFY-UHFFFAOYSA-N azanylidynevanadium Chemical compound [V]#N SKKMWRVAJNPLFY-UHFFFAOYSA-N 0.000 description 1
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- 239000000835 fiber Substances 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical class [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
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- 229910021645 metal ion Inorganic materials 0.000 description 1
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- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- JKJKPRIBNYTIFH-UHFFFAOYSA-N phosphanylidynevanadium Chemical compound [V]#P JKJKPRIBNYTIFH-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a nitrogen and phosphorus codoped vanadium oxide/carbon self-supporting electrode material and a preparation method and application thereof, wherein the method comprises the steps of dissolving a vanadium source and a carbon source compound into an organic solution at a certain temperature to obtain a uniform solution, maintaining the temperature, and then adding a nitrogen source and a phosphorus source compound into the solution at intervals to obtain a uniform spinning solution; obtaining a nanofiber film after electrostatic spinning, and then drying to remove the organic solution to obtain a self-supporting electrode precursor; pre-oxidizing the self-supporting electrode precursor, and then calcining at high temperature for a certain time to obtain a proper amount of oxygen vacancy-doped VO/C self-supporting electrode material. The electrode material has higher specific surface area, and a proper amount of oxygen vacancy defects and nitrogen and phosphorus heteroatoms, and presents long service life, high specific capacity, excellent cycle stability and rate capability.
Description
Technical Field
The invention relates to the field of zinc ion battery application, in particular to a nitrogen and phosphorus co-doped vanadium oxide/carbon self-supporting electrode material and a preparation method and application thereof.
Background
The rechargeable battery energy storage technology with high energy density, low cost and intrinsic safety is always an urgent need in the fields of electric automobiles, smart power grids, micro-nano devices and the like. In view of the high theoretical capacity of zinc metal (820mAh g) -1 ) The advantages of low cost and low oxidation-reduction potential (-0.762V vs. SHE), high chemical stability of the aqueous electrolyte and the like, and the aqueous zinc ion battery is considered to be the next generation of energy storage technology with high market competitiveness in recent years. The positive electrode material generally plays a crucial role in determining the energy and power density of the battery. Therefore, the development of the positive electrode material has become an important support point for the development of the aqueous zinc ion battery. To date, a variety of candidate materials have been successfully developed, mainly including vanadium oxide, manganese oxide, prussian blue analog, and organic matter, and the like. Among them, vanadium oxide exhibits a high specific capacity due to its advantage of multiple electron transfer. However, most vanadium oxides generally exhibit the disadvantages of easy structural collapse, easy dissolution of vanadium elements, and the like, resulting in poor cycle stability. Therefore, how to improve the stability of the vanadium oxide crystal structure is a key point for obtaining a long-life aqueous zinc ion battery.
Oxygen vacancy introduction and non-metal heteroatom doping are always the most important strategies for improving the performance of transition metal oxides, and the transition metal oxides are widely concerned in the fields of metal ion batteries, air batteries, supercapacitors, catalysis and the like. On one hand, oxygen vacancy is introduced, so that reactive sites can be increased, electronic structures can be modified, the generation energy can be reduced, and the like; on the other hand, doping non-metal heteroatoms can not only provide additional energy levels, increase reactive sites and reduce reaction energy barriers, but also form heteroconfigurational interfaces, such as a heterostructural interface between vanadium oxide and vanadium nitride, so as to improve zinc storage capacity and reaction kinetics. Although the heteroatom-doped transition metal oxide can introduce oxygen vacancy and heteroatom at the same time, the oxygen vacancy content is difficult to regulate in the doping process, so that the electrochemical performance of the heteroatom-doped transition metal oxide electrode is difficult to substantially improve.
Disclosure of Invention
The invention aims to provide a nitrogen and phosphorus co-doped vanadium oxide/carbon self-supporting electrode material which contains a proper amount of oxygen vacancies and has long service life, and a preparation method and application thereof. The preparation method is mainly characterized in that the electrode material is prepared and obtained by electrostatic spinning and high-temperature calcination technologies and further regulating and controlling the content of nitrogen and phosphorus heteroatoms, and the obtained electrode material not only has a higher specific surface area, but also has a proper amount of oxygen vacancy defects and nitrogen and phosphorus heteroatoms, so that the electrode material has the characteristic of long service life. Compared with single heteroatom doping, the double heteroatom doping provided by the invention has a more excellent synergistic effect in the aspect of improving the overall electrochemical performance. Meanwhile, the electrode material obtained by the invention has a proper amount of oxygen vacancies, which is more beneficial to stabilizing the VO structure; the specific surface area of the electrode material is high, so that zinc storage sites can be increased, and high specific capacity can be obtained; the proper amount of oxygen vacancies and heteroatoms reduce the electrostatic interaction between divalent zinc ions and a VO phase crystal structure, and are more favorable for constructing a vanadium oxide-vanadium nitride (vanadium phosphide) heterostructure interface, so that the obtained cycle stability and rate capability are more excellent.
In order to achieve the purpose, the invention at least adopts the following technical scheme:
a preparation method of a nitrogen and phosphorus co-doped vanadium oxide/carbon self-supporting electrode material comprises the following steps:
dispersing a vanadium source and a carbon source compound into an organic solution at a certain temperature to obtain a uniform solution, maintaining the temperature, and then adding a nitrogen source and a phosphorus source compound into the solution at certain intervals to obtain a uniform spinning solution;
stretching and thinning the spinning solution through electrostatic spinning to obtain a nanofiber film, and drying at a certain temperature to remove an organic solution to obtain a self-supporting electrode precursor;
and placing the self-supporting electrode precursor in an air atmosphere for pre-oxidation at a certain temperature, and then calcining at a high temperature in a specific atmosphere for a certain time to obtain a proper amount of oxygen vacancy nitrogen and phosphorus co-doped VO/C self-supporting electrode material.
The vanadium source is at least one of vanadium acetylacetonate and vanadyl acetylacetonate; the carbon source is one of polyacrylonitrile and polyvinylidene fluoride; the organic solvent is N, N-dimethylformamide; the mass ratio of the vanadium source to the carbon source is 1.0-2.0, and the mass ratio of the carbon source to the organic solution is 0.08-0.12.
The high specific capacity advantage of vanadium oxide can be reduced by the high content of nitrogen and phosphorus heteroatoms, so that the regulation and control of the content of the nitrogen and phosphorus heteroatoms is one of the keys of the electrode material for obtaining high zinc storage capacity. The nitrogen source is at least one of urea, melamine, ammonium nitrate and ammonium sulfate; the mass ratio of the nitrogen source to the vanadium source compound is 0.25-0.4; the phosphorus source compound is at least one of melamine phosphate, triphenylphosphine and organic phosphoric acid, and the mass ratio of the phosphorus source compound to the vanadium source compound is 0.12-0.22.
In the step of obtaining the uniform spinning solution, the temperature is 40-60 ℃, the dispersing condition is that stirring is carried out at the speed of 300-600 r/min, and the time required for dissolving the vanadium source and the carbon source compound is 3-6 h; the time required for dispersing the nitrogen source is 5-8 h; the time required for dispersing the phosphorus source is 5-8 h.
In the step of obtaining the uniform spinning solution, the dispersion condition is that ultrasonic dispersion is carried out at the temperature of 20-30 ℃, and the time required by the dispersion of the nitrogen source is 2.5-4 h; the time required for dispersing the phosphorus source is 2.5-4 hours.
The electrostatic spinning process parameters are as follows: the positive voltage is 13 to 17kV, and the negative voltage is 0 to-0.1 kV; a single spray head is adopted; the filament collecting device is a roller, and the rotating speed is 250 r/min; the working distance is 17-20 cm; the type of the spinning needle head is 18-20G; the spinning humidity is less than 20 percent, and the temperature is 30 ℃ below zero.
The temperature for drying and removing the organic solution is 40-70 ℃, and the drying time is 3-8 h.
The pre-oxidation temperature is 200-250 ℃, and the pre-oxidation time is 2 h.
And the high-temperature calcining atmosphere adopts argon-hydrogen mixed gas. Compared with calcination in argon or nitrogen atmosphere and calcination in argon-hydrogen mixed atmosphere, the electrode material can obtain a proper amount of oxygen vacancies, and further the VO phase crystal structure can be further stabilized, so that the long service life is obtained.
The high-temperature calcination time is 1-1.5 h, and the high-temperature calcination temperature is 750-850 ℃.
The nitrogen and phosphorus co-doped vanadium oxide/carbon self-supporting electrode material is obtained by adopting the preparation method.
The nitrogen and phosphorus co-doped vanadium oxide/carbon self-supporting electrode material is applied to an organic or aqueous zinc ion battery.
Drawings
FIG. 1 is a flow chart of the preparation of a nitrogen-phosphorus co-doped vanadium oxide/carbon self-supporting electrode material according to an embodiment of the present invention.
Fig. 2 is an XRD pattern of the electrode material prepared in example 1 of the present invention.
FIG. 3 is an EPR map of the electrode material prepared in example 1 of the present invention.
Fig. 4 is an SEM image of the electrode material prepared in example 1 of the present invention.
FIG. 5 is a graph (20A/g) showing the cycle performance of an aqueous zinc-ion battery assembled with the electrode material prepared in example 1 of the present invention as a positive electrode material.
Fig. 6 is a graph showing the rate performance of an aqueous zinc ion battery assembled by using the electrode material prepared in example 1 of the present invention as a positive electrode material.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely with reference to the accompanying drawings, and the described embodiments are only a part of the embodiments of the present invention, but not all of the embodiments. Based on the embodiments of the present invention, other embodiments obtained by persons of ordinary skill in the art without any creative effort belong to the protection scope of the present invention. The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials, unless otherwise indicated, are commercially available from a public disclosure.
The use of terms such as "having," "containing," "including," and the like in this specification is an open-ended term meaning the presence of stated elements or features, but does not preclude additional elements or features. Unless the context clearly dictates otherwise.
One embodiment of the invention provides a preparation method of a nitrogen-phosphorus co-doped vanadium oxide/carbon self-supporting electrode material, which comprises a series of steps of spinning solution preparation, electrostatic spinning, organic solution removal, pre-oxidation and high-temperature calcination, as shown in figure 1.
Example 1
Preparing a spinning solution: 0.6g of vanadium acetylacetonate and 0.4g of polyacrylonitrile are added into an organic solution in which 1g N, N-dimethylformamide is dissolved, and the mixture is magnetically stirred for 6 hours at a constant temperature of 50 ℃ and the stirring speed of 500r/min to prepare a uniform solution. Subsequently, 0.2g of melamine and 0.1g of melamine phosphate were added to the above solution every 6 hours while maintaining the temperature and the stirring speed, respectively, to prepare a uniform spinning solution, and the order of addition of melamine and melamine phosphate was not limited.
Electrostatic spinning: the spinning solution was transferred to a needle tube to carry out spinning, thereby preparing a film. Wherein the working distance is 17cm, the humidity is 17%, the temperature is 32 ℃, the applied positive voltage is 16kV, the negative voltage is-0.05 kV, the rotating speed of the roller is 250r/min, and the model of the spinning needle is 19G.
Removing the organic solution: drying at 60 deg.C for 6h to remove organic solvent.
Pre-oxidation: and cutting the collected film, putting the cut film into a muffle furnace, and pre-oxidizing the film for 2 hours at 250 ℃ in an air atmosphere.
High-temperature calcination: then calcining for 1.5H at 800 ℃ in the atmosphere of argon-hydrogen mixed gas to obtain the nitrogen-phosphorus co-doped VO/C self-supporting (recorded as N, P-VO/C-H) electrode material.
Comparative example
Preparing a spinning solution: 0.6g of vanadium acetylacetonate and 0.4g of polyacrylonitrile are added into an organic solution in which 1g N, N-dimethylformamide is dissolved, and the mixture is magnetically stirred for 6 hours at a constant temperature of 50 ℃ and the stirring speed of 500r/min to prepare a uniform solution. Subsequently, 0.2g of melamine and 0.1g of melamine phosphate were added to the above solution every 6 hours while maintaining the temperature and the stirring speed, respectively, to prepare a uniform spinning solution, and the order of addition of melamine and melamine phosphate was not limited.
Electrostatic spinning: the spinning solution was transferred to a needle tube to carry out spinning, thereby preparing a film. Wherein the working distance is 17cm, the humidity is 17%, the temperature is 32 ℃, the applied positive voltage is 16kV, the negative voltage is-0.05 kV, the rotating speed of the roller is 250r/min, and the model of the spinning needle is 19G.
Removing the organic solution: drying at 60 deg.C for 6h to remove organic solvent.
Pre-oxidation: and cutting the collected film, putting the cut film into a muffle furnace, and pre-oxidizing the film for 2 hours at 250 ℃ in an air atmosphere.
High-temperature calcination: then calcining for 1.5h at 800 ℃ under the argon atmosphere to obtain the nitrogen and phosphorus co-doped VO/C self-supporting (recorded as N, P-VO/C) electrode material with high oxygen vacancy content.
Example 2
Preparing a spinning solution: 0.6g of vanadium acetylacetonate and 0.4g of polyacrylonitrile are added into an organic solution in which 1g N, N-dimethylformamide is dissolved, and the mixture is magnetically stirred for 6 hours at a constant temperature of 50 ℃ and the stirring speed of 500r/min to prepare a uniform solution. Subsequently, 0.2g of melamine and 0.1g of melamine phosphate were added to the above solution every 6 hours while maintaining the temperature and the stirring speed, respectively, to prepare a uniform spinning solution, and the order of addition of melamine and melamine phosphate was not limited.
Electrostatic spinning: the spinning solution was transferred to a needle tube to carry out spinning, thereby preparing a film. Wherein the working distance is 17cm, the humidity is 17%, the temperature is 32 ℃, the applied positive voltage is 16kV, the negative voltage is-0.05 kV, the rotating speed of the roller is 250r/min, and the model of the spinning needle is 19G.
Removing the organic solution: drying at 60 deg.C for 6h to remove organic solvent.
Pre-oxidation: and cutting the collected film, putting the cut film into a muffle furnace, and pre-oxidizing the film for 2 hours at 250 ℃ in an air atmosphere.
High-temperature calcination: then calcining for 1.5H at 750 ℃ in an argon-hydrogen mixed gas atmosphere to obtain the nitrogen-phosphorus co-doped VO/C self-supporting (recorded as N, P-VO/C-H) electrode material.
Example 3
Preparing a spinning solution: 0.6g of vanadium acetylacetonate and 0.4g of polyacrylonitrile are added into an organic solution in which 1g N, N-dimethylformamide is dissolved, and the mixture is magnetically stirred for 6 hours at a constant temperature of 50 ℃ and the stirring speed is 500r/min to prepare a uniform solution. Subsequently, 0.2g of melamine and 0.12g of melamine phosphate were added to the above solution every 6 hours while maintaining the temperature and the stirring speed, respectively, to prepare a uniform spinning solution, and the order of addition of melamine and melamine phosphate was not limited.
Electrostatic spinning: the spinning solution was transferred to a needle tube to carry out spinning, thereby preparing a film. Wherein the working distance is 17cm, the humidity is 17%, the temperature is 32 ℃, the applied positive voltage is 16kV, the negative voltage is-0.05 kV, the rotating speed of the roller is 250r/min, and the model of the spinning needle is 19G.
Removing the organic solution: drying at 60 deg.C for 6h to remove organic solvent.
Pre-oxidation: and cutting the collected film, putting the cut film into a muffle furnace, and pre-oxidizing the film for 2 hours at 250 ℃ in an air atmosphere.
High-temperature calcination: then calcining for 1.5H at 800 ℃ in the atmosphere of argon-hydrogen mixed gas to obtain the nitrogen-phosphorus co-doped VO/C self-supporting (recorded as N, P-VO/C-H) electrode material.
Example 4
Preparing a spinning solution: preparing a spinning solution: 0.6g of vanadium acetylacetonate and 0.4g of polyacrylonitrile are added into an organic solution in which 1g N, N-dimethylformamide is dissolved, and the mixture is magnetically stirred for 6 hours at a constant temperature of 50 ℃ and the stirring speed is 500r/min to prepare a uniform solution. Subsequently, 0.2g of melamine and 0.1g of melamine phosphate were added to the above solution every 6 hours while maintaining the temperature and the stirring speed, respectively, to prepare a uniform spinning solution, and the order of addition of melamine and melamine phosphate was not limited.
Electrostatic spinning: the spinning solution was transferred to a needle tube to carry out spinning, thereby preparing a film. Wherein the working distance is 17cm, the humidity is 17%, the temperature is 32 ℃, the applied positive voltage is 16kV, the negative voltage is-0.05 kV, the rotating speed of the roller is 250r/min, and the model of the spinning needle is 19G.
Removing the organic solution: drying at 60 deg.C for 6h to remove organic solvent.
Pre-oxidation: and cutting the collected film, putting the cut film into a muffle furnace, and pre-oxidizing the film for 2 hours at 250 ℃ in an air atmosphere.
High-temperature calcination: then calcining for 1H at 800 ℃ in the atmosphere of argon-hydrogen mixed gas to obtain the nitrogen-phosphorus co-doped VO/C self-supporting (noted as: N, P-VO/C-H) electrode material.
FIG. 2 is a XRD (X-ray diffraction) chart of the N, P-VO/C electrode material prepared in the comparative example and the N, P-VO/C-H film prepared in example 1, and it can be seen that the diffraction peaks of the two films after comparison correspond to the VO phase PDF card (JCPDS 75-0048); FIG. 3 is an EPR curve of a sample of the present invention showing that N, P-VO/C-H has a moderate oxygen vacancy concentration compared to N, P-VO/C; FIG. 4 is an SEM topography of N, P-VO/C-H, and it can be seen that the self-supporting electrode material is composed of fibers with a diameter of about 700 nm.
An aqueous zinc ion battery was assembled using the electrode material prepared in example 1 as a positive electrode, a zinc sheet as a negative electrode, 3M zinc trifluoromethanesulfonate as an electrolyte, and glass fibers as a separator. And (3) assembling the water system zinc ion battery by taking the electrode material prepared in the comparative example as a positive electrode, a zinc sheet as a negative electrode, 3M zinc trifluoromethanesulfonate as electrolyte and glass fiber as a diaphragm to perform performance test. FIG. 5 is 20A g -1 Long-term cycling stability diagram of electrode under current density, N, P-VO/C-H electrode at 20A g -1 After 10000 weeks of cycling at a current density of (3), 94.7mA hr g was exhibited -1 High specific discharge capacity and capacity retention of 98.2%. FIG. 6 shows electrodes of example 1 and comparative example at 1 to 3, 5, 10, 30, 60 or even ultra-high magnification of 100Ag -1 The average specific capacities of the N, P-VO/C-H electrodes are 176, 151, 141, 104, 98.3, 70.3 and 52.1mA H g respectively -1 The advantages of the N, P-VO/C-H nanofiber electrode are fully proved.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of a nitrogen and phosphorus co-doped vanadium oxide/carbon self-supporting electrode material is characterized by comprising the following steps:
dissolving a vanadium source and a carbon source compound into an organic solution at a certain temperature to obtain a uniform solution, maintaining the temperature, and then adding a nitrogen source and a phosphorus source compound into the solution at certain intervals to obtain a uniform spinning solution;
stretching and thinning the spinning solution through electrostatic spinning to obtain a nanofiber film, and drying at a certain temperature to remove an organic solution to obtain a self-supporting electrode precursor;
and placing the self-supporting electrode precursor in an air atmosphere for pre-oxidation at a certain temperature, and then calcining at a high temperature in a specific atmosphere for a certain time to obtain a proper amount of oxygen vacancy nitrogen and phosphorus co-doped VO/C self-supporting electrode material.
2. The preparation method according to claim 1, wherein the vanadium source is at least one of vanadium acetylacetonate and vanadyl acetylacetonate; the carbon source is one of polyacrylonitrile and polyvinylidene fluoride; the organic solvent is N, N-dimethylformamide; the mass ratio of the vanadium source to the carbon source is 1.0-2.0, and the mass ratio of the carbon source to the organic solution is 0.08-0.12.
3. The production method according to claim 1 or 2, wherein the nitrogen source is at least one selected from urea, melamine, ammonium nitrate and ammonium sulfate; the mass ratio of the nitrogen source to the vanadium source compound is 0.25-0.4; the phosphorus source compound is at least one of melamine phosphate, triphenylphosphine and organic phosphoric acid, and the mass ratio of the phosphorus source compound to the vanadium source compound is 0.12-0.22.
4. The preparation method according to claim 3, wherein in the step of obtaining a uniform spinning solution, the temperature is 40-60 ℃, the dispersion condition is that stirring is carried out at a speed of 300-600 r/min, and the time required for dissolving the vanadium source and carbon source compounds is 3-6 h; the time required for dispersing the nitrogen source is 5-8 h; the time required for dispersing the phosphorus source is 5-8 h.
5. The preparation method according to claim 4, wherein in the step of obtaining a uniform spinning solution, the dispersion conditions are ultrasonic dispersion at a temperature of 20 to 30 ℃, and the time required for dissolving and dispersing the nitrogen source is 2.5 to 4 hours; the time required for dissolving and dispersing the phosphorus source is 2.5-4 h.
6. The method according to claim 4 or 5, wherein the electrostatic spinning process parameters are as follows: the positive voltage is 13 to 17kV, and the negative voltage is 0 to-0.1 kV; a single spray head is adopted; the filament collecting device is a roller, and the rotating speed is 250 r/min; the working distance is 17-20 cm; the type of the spinning needle head is 18-20G; the spinning humidity is less than 20 percent, and the temperature is 30 ℃ below zero.
7. The preparation method according to claim 1, 2, 4 or 5, characterized in that the temperature for drying to remove the organic solution is 40-70 ℃ and the drying time is 3-8 h.
8. The preparation method according to claim 1, 2, 4 or 5, characterized in that the pre-oxidation temperature is 200-250 ℃ and the pre-oxidation time is-2 h; the high-temperature calcination time is 1-1.5 h, and the high-temperature calcination temperature is 750-850 ℃; the atmosphere of the high-temperature calcination is a mixed gas of argon and hydrogen.
9. A nitrogen-phosphorus co-doped vanadium oxide/carbon self-supporting electrode material, which is obtained by the preparation method of any one of claims 1 to 8.
10. The use of the nitrogen-phosphorus co-doped vanadium oxide/carbon self-supporting electrode material of claim 9 in an organic or aqueous zinc ion battery.
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